JP2021524664A - Discharge chamber, and ionization devices, ionization methods and ionization systems using it - Google Patents

Abstract

Specific configurations of a plasma discharge chamber and a plasma ionization source comprising a plasma discharge chamber are described. In some embodiments, the discharge chamber comprises a conductive area and is configured to maintain plasma discharge within the discharge chamber. In another embodiment, the discharge chamber comprises at least one inlet configured to receive plasma gas and at least one outlet configured to provide ionized analysts from the discharge chamber. Systems and methods that use the discharge chamber are also described. [Selection diagram] Fig. 1

Description

Preferred Application This application is a related application of US Provisional Application No. 62 / 673,513 filed on May 18, 2018, claiming priority over this provisional application and the interests of this provisional application. Yes, the entire disclosure of this provisional application is incorporated herein by reference.

The techniques described herein relate to ionization devices, ionization methods and systems. More specifically, some configurations of plasma discharge ion sources, as well as systems and methods using them, will be described.

Ionization methods are often used to analyze various analysts. Ionization of the analyte can often result in a large amount of fragmentation.

Certain embodiments, embodiments, configurations and features of ionization devices, ionization methods and ionization systems are described herein.

In one aspect, a plasma discharge ionization source is provided. In certain configurations, the ionization source comprises a discharge chamber that is configured to be electrically coupled to a power source and is configured to maintain plasma discharge within the discharge chamber, where the discharge chamber is a plasma gas. It comprises at least one inlet configured to accept the plasma and at least one outlet configured to provide ionized analysts from the discharge chamber.

In certain embodiments, the plasma discharge ion source further comprises at least one bend between at least one inlet and at least one outlet, with at least one bend passing through at least one outlet. It is configured to reduce the number of semi-stable atoms and free electrons and photons leaving the discharge chamber. In some embodiments, at least one bend is configured as a bend of about 90 degrees. In other embodiments, the plasma discharge ion source further comprises a second bend located upstream of at least one bend or downstream of at least one bend.

In some examples, the plasma discharge ion source further comprises a first electrode electrically coupled to the discharge chamber, the first electrode being configured to be electrically coupled to the power source. In another embodiment, the first electrode is located within at least one inlet of the discharge chamber. In some embodiments, the plasma discharge ion source further comprises a second electrode electrically coupled to the discharge chamber.

In some embodiments, the discharge chamber comprises one or more conductive materials such as stainless steel, tungsten, nickel-chromium alloys, nickel-chromium molybdenum alloys, titanium, titanium alloys, and combinations thereof.

In certain embodiments, the inlet is configured to receive the plasma gas and the sample containing the analite at the same time. In another embodiment, the plasma discharge ionization source further comprises a second inlet separate from the inlet, the second inlet being configured to feed the discharge chamber with a sample containing the analite. In some embodiments, the discharge chamber has a first area adjacent to at least one inlet, a third area adjacent to at least one outlet, and a first area between the first and third areas. It has two areas.

In another embodiment, the average inner diameter of the third area is larger than the average inner diameter of the second area. In some embodiments, the average inner diameter of the second area is greater than the average inner diameter of the first area.

In another embodiment, the discharge chamber further comprises a second inlet configured to receive a second plasma gas. In certain embodiments, the discharge chamber is configured to maintain plasma discharge without any inductive coupling.

In some configurations, the plasma discharge ion source further comprises a second discharge chamber fluidly coupled to the discharge chamber, the second discharge chamber having an inlet area and an outlet area of the second discharge chamber. It is provided with at least one curved portion in between. In certain embodiments, at least one bend in the second discharge chamber has a different geometry than at least one bend in the discharge chamber.

In certain embodiments, the plasma discharge ion source further comprises an electrode electrically coupled to a second discharge chamber. In some embodiments, the second discharge chamber is configured to maintain plasma discharge with a second plasma gas that is different from the plasma gas. In one particular embodiment, the discharge chamber may be configured to receive two or more different plasma gases and use the different plasma gases to selectively ionize different different analyte species.

In another aspect, the mass spectrometer system comprises a plasma discharge ionization source. The plasma discharge ionization source may include a discharge chamber configured to be electrically coupled to a power source, the discharge chamber being configured to maintain plasma discharge within the discharge chamber, and the discharge chamber being plasma. It comprises at least one inlet configured to receive the gas and at least one outlet configured to provide ionized analysts from the discharge chamber. The mass spectrometer system may also include a mass spectrometer that is fluidly coupled to at least one outlet of the discharge chamber and is configured to receive ionized analysts from the discharge chamber.

In certain embodiments, the discharge chamber further comprises a first electrode electrically coupled to the discharge chamber, the first electrode being configured to be electrically coupled to a power source. In some embodiments, the discharge chamber is directly coupled to the inlet orifice of the mass spectrometer.

In another embodiment, the mass spectrometer comprises at least one quadrupole assembly fluidly coupled to the outlet of the discharge chamber. In some examples, the mass spectrometer comprises a triple quadrupole assembly. In another example, the mass spectrometer system comprises at least one pumping stage between the outlet of the discharge chamber and the inlet of the triple quadrupole assembly. In some embodiments, the first quadrupole assembly of the triple quadrupole assembly is fluidly coupled to at least one pumping stage and the first quadrupole assembly is configured as a mass filter. NS. In another example, the second quadrupole assembly of the triple quadrupole assembly is fluidly coupled to the first quadrupole assembly and the second quadrupole assembly is the collision quadrupole assembly. It is configured as. In some embodiments, the third quadrupole assembly of the triple quadrupole assembly is fluidly coupled to the second quadrupole assembly and the third quadrupole assembly is configured as a mass filter. Will be done.

In some embodiments, the mass spectrometer system further comprises a detector fluidly coupled to a third quadrupole assembly. In certain embodiments, the mass analyzer system further comprises a processor electrically coupled to the discharge chamber, the processor applying a first voltage to the discharge chamber to maintain plasma discharge within the discharge chamber. Configured to supply. In some embodiments, the processor is configured to supply a second voltage that is different from the first voltage in order to maintain the plasma discharge in the discharge chamber. In some configurations, the processor is further configured to supply plasma gas to the discharge chamber. In certain embodiments, the processor is further configured to supply a second plasma gas, which is different from the plasma gas described above, to the discharge chamber.

In certain embodiments, the mass spectrometer discharge chamber comprises a first area adjacent to at least one inlet, a third area adjacent to at least one outlet, and a first and third area. A second area between may be provided. In another embodiment, the average inner diameter of the third area is larger than the average inner diameter of the second area, and the average inner diameter of the second area is larger than the average inner diameter of the first area.

In some embodiments, the mass spectrometer discharge chamber further comprises at least one bend between at least one inlet and at least one outlet, with at least one bend having at least one outlet. It is configured to reduce the number of semi-stable atoms and free electrons that pass through and exit the discharge chamber.

In one particular embodiment, the mass analyzer system further comprises a second discharge chamber fluidly coupled to the discharge chamber, the second discharge chamber having an inlet area and an outlet area of the second discharge chamber. At least one curved portion is provided between the two.

In some embodiments, the mass spectrometer system further comprises a chromatography system fluidly coupled to at least one inlet of the discharge chamber. In certain embodiments, the chromatography system is configured as a gas chromatography system or a liquid chromatography system.

In another aspect, the method comprises ionizing the analyte by introducing it into a plasma discharge maintained in a discharge chamber comprising a first electrode, the discharge chamber having at least one inlet. And with at least one outlet, the discharge chamber by supplying a voltage to the first electrode in the presence of plasma gas introduced into the discharge chamber through at least one inlet of the discharge chamber. Maintained within.

In certain embodiments, the method comprises configuring the first electrode to be located within at least one inlet of the discharge chamber. In some embodiments, the method comprises supplying the first electrode with a DC voltage of about +/- 10V to about +/- 5000V. In another embodiment, the method comprises supplying the first electrode with an AC voltage of about +/- 20 volts to about +/- 3000 volts. In some examples, the method comprises supplying a radio frequency current to the first electrode, the frequency of the radio frequency being from about 100 Hz to about 10 MHz. The voltages and frequencies provided herein are merely explanatory and other voltages and frequencies will be selected by one of ordinary skill in the art to benefit from the present disclosure.

In another embodiment, the method comprises maintaining the plasma discharge in the discharge chamber at a pressure suitable for maintaining the plasma discharge, for example, one embodiment has a pressure of ^{about 10-3 to 100 torr.} Can be used. In some embodiments, the method comprises providing plasma discharge using a plasma gas flow rate of 500 sccm or less, but flow rates other than this exemplary flow rate can also be used.

In some embodiments, the method comprises a first area adjacent to at least one entrance, a third area adjacent to at least one exit, and a first area between the first and third areas. The average inner diameter of the third area is larger than the average inner diameter of the second area, including forming the discharge chamber in the second area.

In certain embodiments, the method facilitates the production of parental analite ions in ionized analysts to allow quantification of the analysts using the mass vs. charge peak intensity of the parental analite ions. Includes selecting the supply voltage.

In some embodiments, the method comprises monitoring the current delivered to the first electrode to determine if plasma discharge is maintained within the discharge chamber. In certain embodiments, the method comprises using an optical sensor to determine if plasma discharge is maintained within the discharge chamber.

In some configurations, the plasma gas is helium, neon, argon, krypton, xenone, nitrogen, nitric oxide, ammonia, oxygen, air, compressed air, hydrogen, methane, carbon monoxide, carbon dioxide, nitrous oxide, And one or more of nitric oxide. These descriptive plasma gases are provided by way of example and are not intended to exclude other plasma gases that may be used as well, such as rare earth gases, rare earth gas mixtures and the like.

In one particular embodiment, the method introduces an analyte into the discharge chamber to ionize the introduced analyst using a first plasma gas and a second analog in the discharge chamber. Allowing the ionized analyst to exit the discharge chamber through at least one outlet prior to introduction into the discharge chamber and introducing a second analyst into the discharge chamber to introduce the second Includes the ionizing of the analysts with a second plasma gas that is different from the first plasma gas. In some examples, the method allows the ionized second analyst to exit the discharge chamber through at least one outlet before introducing the third analyst into the discharge chamber. In addition, a third analyzer is introduced into the discharge chamber, and the introduced third analyzer is ionized using a first plasma gas and a third plasma gas different from the second plasma gas. Including to do. Each of the first plasma gas and the second plasma gas independently helium, neon, argon, krypton, xenone, nitrogen, nitrous oxide, ammonia, oxygen, air, compressed air, hydrogen, methane, monoxide. It can be one or more of carbon, carbon dioxide, nitrous oxide, and nitrogen dioxide.

In one particular embodiment, the method introduces an analyzer into a discharge chamber and ionizes the introduced analog using a first voltage supplied to at least one electrode. Allowing the ionized analyst to exit the discharge chamber through at least one outlet and introducing a second analyst into the discharge chamber before introducing the second analyst into the discharge chamber. The introduced second analyzer is ionized using a second voltage different from the first voltage. In some embodiments, the method allows the ionized second analyst to exit the discharge chamber through at least one outlet before introducing the third analyst into the discharge chamber. And to introduce a third analyst into the discharge chamber and ionize the introduced third analyst using a third voltage different from the first voltage and the second voltage. And include. In some embodiments, the method comprises altering the composition of the plasma gas prior to introducing the second analyst into the discharge chamber.

In another embodiment, the method comprises configuring the discharge chamber to include at least one bend between at least one inlet and at least one outlet.

In some embodiments, the method comprises coupling a discharge chamber to a second discharge chamber, the second discharge chamber being electrically coupled to a second electrode and a second discharge. The chamber comprises at least one inlet and at least one outlet, and plasma discharge is maintained in the second discharge chamber by supplying voltage to the second electrode in the presence of plasma gas. NS. In some configurations, the second discharge chamber may consist of at least one bend between at least one inlet of the second discharge chamber and at least one outlet of the second discharge chamber. can. The methods described herein can be used to maintain plasma discharge in the discharge chamber without any inductive coupling.

In an additional aspect, a kit comprising one or more of the plasma discharge ion sources described herein is provided, and the instructions for using the plasma discharge ion source provide plasma discharge within the discharge chamber.

In another aspect, a method of promoting ionization of the analite is described. In some embodiments, the method is to provide a discharge chamber that is configured to maintain plasma discharge within the discharge chamber, at least the discharge chamber is configured to couple to a power source. The discharge chamber is configured to be electrically coupled to one electrode, comprising providing a discharge chamber further comprising at least one inlet and at least one outlet, the discharge chamber having at least one. It is configured to use the voltage supplied to the electrodes to maintain a plasma discharge in the discharge chamber.

In a further aspect, a method of facilitating ionization of the analyte is to provide a discharge chamber that is configured to maintain plasma discharge within the discharge chamber, the discharge chamber being configured to couple to a power source. It is configured to be electrically coupled to at least one electrode. The discharge chamber may further comprise at least one inlet, at least one outlet, and optionally at least one bend between at least one inlet and at least one outlet. The discharge chamber can be configured to maintain plasma discharge within the discharge chamber using the voltage supplied to at least one electrode.

In another aspect, the method of quantifying the announcer in the sample is from ionization of the analyzer after introducing the announcer into the plasma discharge generated in the discharge chamber by using a plasma gas flow rate of 500 sccm or less. Includes measuring the peak intensity of the parental analite ions produced. In some embodiments, the plasma gas may be selected to increase the production of parental analite ions using the generated plasma discharge.

In a further aspect, a method of ionizing the analytes to increase the production of parental analyte ions uses the plasma gas supplied to the discharge chamber and the voltage supplied to the discharge chamber into the discharge chamber. Includes the introduction of analysts into the sustained plasma discharge. In some configurations, the plasma discharge can be maintained in the discharge chamber using a plasma gas stream of 500 sccm or less. In some examples, the plasma discharge comprises an average temperature of about 2000 Kelvin or less.

In another aspect, a plasma discharge containing an average temperature of about 2000 Kelvin or less is described. In some embodiments, the plasma discharge can be maintained in the discharge chamber using the voltage delivered to the discharge chamber in the presence of plasma gas supplied at a plasma gas flow rate of 500 sccm or less.

In another aspect, a plasma discharge is provided that is configured to provide both positive and negative analyze ions without changing the voltage supplied to maintain the plasma discharge.

Further embodiments, configurations, embodiments and examples will be described in more detail below.

Specific specific configurations of devices, systems and methods are described below with reference to the accompanying figures.

FIG. 3 is an explanatory view of a discharge chamber or discharge tube configured to maintain a discharge ion source according to a particular embodiment. It is explanatory drawing which shows the electrode arranged in the inlet of the discharge chamber by a specific embodiment. It is explanatory drawing which shows the electrode arranged in the inlet of the discharge chamber, and the 2nd electrode existing in the discharge chamber by a specific embodiment. It is explanatory drawing which shows the discharge chamber with the sharp bending part by some embodiments. It is explanatory drawing which shows the discharge chamber with the gentle bending part according to some embodiments. FIG. 5 is an explanatory view of a discharge chamber with two bends according to a particular embodiment. FIG. 5 is an explanatory view of a discharge chamber having three bends according to some embodiments. FIG. 6 is an explanatory view of a discharge chamber with two bends of different configurations, according to some embodiments. It is explanatory drawing of the discharge chamber with two inlets by some configurations. FIG. 3 is another explanatory view of a discharge chamber with two inlets according to a particular embodiment. It is explanatory drawing of the discharge chamber provided with two outlets by some examples. It is explanatory drawing of the straight type chamber with a variable diameter by some examples. Another explanatory view of a straight chamber with variable diameters in several configurations. It is explanatory drawing of the straight type chamber with a variable diameter by some examples. FIG. 3 is an explanatory view of a curved chamber having a variable diameter according to a specific example. It is explanatory drawing of two discharge chambers connected to each other by some examples. It is another explanatory view of two discharge chambers coupled to each other according to some examples. It is explanatory drawing of two parallel discharge chambers by some examples. It is explanatory drawing of the discharge chamber provided with the optical window by some examples. FIG. 6 is an explanatory diagram of a gas chromatography system fluidly coupled to a discharge chamber according to some examples. FIG. 6 is an explanatory diagram of a liquid chromatography system fluidly coupled to a discharge chamber according to some examples. FIG. 5 is an explanatory diagram of a mass spectrometric system including a discharge chamber according to a specific embodiment. It is explanatory drawing of the discharge chamber by some examples. It is another explanatory view of the discharge chamber according to some examples. FIG. 5 is an explanatory view of a discharge chamber fluidly coupled to a triple quadrupole assembly according to some embodiments. It is a mass spectrum obtained by utilizing electron ionization according to some examples and showing almost no precursor ions. A, B, and C represent mass spectra of various molecules according to a particular embodiment. A and B show mass spectra obtained using the discharge chambers described herein, and C shows the same spectra as in FIG. 14 for comparison.

In light of the benefits of the present disclosure, it will be appreciated by those skilled in the art that dimensions such as length, width, etc. of the Discharge Chamber do not necessarily have to be to scale. The length or width of any one region may vary or may differ from the length or width of any other region. Further, the three-dimensional shape of any one region may be different from the other region and may not necessarily be drawn in the two-dimensional diagram shown.

Specific methods, devices and systems for ionizing devices and systems capable of more gently ionizing one or more analysts are described herein. For example, conventional electron ionization (EI) sources can use very high energies to cause a large amount of fragmentation in a molecule. Excessive fragmentation of molecules to daughter ions can cause duplication of fragments of various analysts, making it difficult to determine the identity and / or amount of the original molecule in the sample. By selecting an ionization device and ionization conditions using the methods and devices described herein, more precursor or parent ions, such as intact molecular ions, are produced without a large amount of fragmentation. Softer ionization can be performed. The presence of increased amounts of precursor ions includes more accurate identification of molecules in unknown samples and improved accuracy in quantifying the amount of each molecule present in unknown samples. It may provide specific attributes not limited to.

Various discharge "tubes" or discharge chambers have been described to illustrate some of the many different configurations that can be used to provide softer ionization of the molecule. The precision dimensions, materials, and shapes of the tubes may vary. In some embodiments, the tube may be, for example, a generally coaxial "straight" tube that is substantially completely unbent, while in other examples the tube is curved, eg, 1. It may have one or more curved portions. The inner diameter of the chamber or tube may be increased or decreased from the inlet end to the outlet end, if desired. In addition, the diameter of one part of the chamber or tube may be increased, followed by the diameter of another part of the tube. The chamber or tube may be optically transparent, optically opaque, or may be provided with one or more optical windows to allow visualization of the plasma discharge in the tube. good. Chambers or tubes can be used to generate both positive and negative ions without the need to change the voltage supplied to maintain the plasma discharge. The chamber or tube may include one, two or more inlets and one, two or more outlets. As will be described in more detail below, more than one part of the chamber or tube may be conductive, but the entire chamber or tube need not be conductive and the various conductive parts of the chamber or tube are required. Can be separated by non-conductive areas depending on the condition. The discharge chamber can be configured to maintain plasma discharge using voltage and plasma gas, for example by supplying a voltage to a portion of the discharge chamber or to an electrode used with the discharge chamber. Plasma discharge can be maintained, for example, without any inductive coupling.

In one particular embodiment, referring to FIG. 1, a straight chamber or tube 100 with a body 105, an inlet 110, and an outlet 115 is shown. The chamber 100 includes a conductive area 112 adjacent to the inlet 110 and a conductive area 117 adjacent to the outlet 115. A voltage can be supplied to the conductive area 112, and the conductive area 117 can be electrically coupled to the ground. When the plasma gas is introduced into the chamber 100 through the inlet 110, the plasma discharge 125 can be maintained in the chamber 100. Depending on the plasma gas used, the discharge 125 may produce metastable atoms and metastable ions. When the analite is introduced into the chamber 100, the analyte molecules collide with electrons, metastable atoms and quasi-stable ions, for example by electron impact, penning ionization and / or charge transfer to form the analyte ions. Can be done. The flow of plasma gas from the inlet 110 to the outlet 115 can transport the analite ions below the chamber 100 and avoid the loss of those analite ions due to collision with the side surface of the chamber 100. Since metastable atoms and free electrons collide with the wall, are redirected, or are removed by other means, they are virtually inaccessible to the downstream components of the system. In general, the difference between the ionization potential of plasma gas and the ionization potential of analite determines the sensitivity of ionization and the degree of fragmentation. By selecting the specific plasma gas to be used, selective ionization can be achieved for various analysts.

In some embodiments, with reference to FIG. 2A, the discharge chamber or discharge tube may be made conductive by electrically coupling an electrode to the inlet end of the chamber. The discharge chamber 200 includes a portion of the conductive area. The electrode 210 is shown to be coupled to the inlet 202 of the discharge chamber 200 via a probe that can act to electrically separate the electrode 210 from the discharge chamber 200. The discharge chamber 200 may be electrically coupled to the chassis ground or ground 225. When a voltage is supplied to the electrode 210 in the presence of plasma gas, the plasma discharge 230 can be maintained within a portion of the chamber 200. The ionization potential of the plasma discharge 230 may be adjusted or altered depending on the supply voltage and / or the supply plasma gas. This adjustment provides a more controlled method for ionizing the molecules introduced into the chamber 200, introducing various analyze molecules into plasma discharges maintained by different plasma gases to analyze. The overall type and nature of the ions produced from the molecule can be modified. The exact dimensions of the electrodes can vary depending on the dimensions of the inlet. For example, electrodes with a diameter of about 1 to 3 mm can be used, the size of which may be reduced or increased depending on the dimensions of the discharge chamber.

In certain embodiments, with reference to FIG. 2B, the discharge tube or discharge chamber may include two or more separation electrodes. The discharge chamber 250 includes a first electrode 260 and a second electrode 265 spatially separated from the first electrode 260. The second electrode 265 may be electrically coupled to the ground or may be supplied with a voltage from a power source. In an embodiment in which a voltage is supplied to each of the first electrode 260 and the second electrode 265, the discharge chamber itself can be electrically coupled to the ground. In some embodiments, the chamber 250 does not have to be conductive and the first electrode 260 and the second electrode 265 may be used to maintain the plasma discharge 275. The voltages supplied to the electrodes 260 and 265 may be the same or different, and may differ depending on the analyze. Similarly, if different plasma gases are introduced into the chamber 250 through the inlet 252, different voltages may be supplied to the electrodes 260 and 265.

In some embodiments, the discharge chamber or discharge tube may include one or more bends that can enhance the removal of metastable atoms and / or free electrons. With reference to FIG. 3A, a discharge chamber 310 comprising a first region 312 and a second region 314 is shown. The inlet 311 exists in the first region 312 and the exit 315 exists in the second region 314. The longitudinal axis of the second region 314 is approximately orthogonal to the longitudinal axis of the first region 312. The chamber of FIG. 3A comprises a "sharp bend" in that the transition from the first region 312 to the second region 314 is rapid. Elimination of interfering species, depending on the particular interfering species present in the analyze sample, as some interfering species can generally choose a linear path from inlet 311 and collide with the orthogonal plane of the second region 314. It may be desirable to include sharp bends in the discharge tube to strengthen it. Analite ions, on the other hand, are carried by the fluidized plasma gas and can exit the chamber through outlet 315. In some embodiments, the inner diameter of the first region 312 and the inner diameter of the second region 314 may be the same. In other embodiments, the average inner diameter of the first region 312 is smaller than the average inner diameter of the second region 314. In yet another example, the average inner diameter of the first region 312 is larger than the average inner diameter of the second region 314. The inner diameter of each of the regions 312 and 314 does not have to be constant along the length of each region, but may be changed as needed. The materials present in the first region 312 and the second region 314 may also be the same or different. The overall shape of regions 312 and 314 may also be the same or different. Moreover, the exact length or other dimensions of the steeply curved area may not be uniform. Although not shown, one or more electrodes can be used in chamber 310, for example, a voltage is supplied to the electrodes, the voltage is utilized in chamber 310, and a plasma discharge occurs within a portion of chamber 310. Can be maintained. The chamber 310 may be conductive or non-conductive, depending on the other components used with the chamber 310. When the electrodes are used in the chamber 310, the electrodes are usually placed adjacent to or near the inlet of the first region 312, but this placement is not required.

In certain embodiments, the discharge chamber or discharge tube may include a gently curved portion instead of a sharply curved portion. With reference to FIG. 3B, a discharge chamber or discharge tube 350 comprising a first region 352 and a second region 354 is shown. An inlet 351 exists in the first region 352 and an exit 355 exists in the second region 354. The longitudinal axis of the second region 354 is also approximately orthogonal to the longitudinal axis of the first region 352. The chamber of FIG. 3B is provided with a "slowly curved portion" in that the transition from the first region 352 to the second region 354 is gradual and is commonly used as a fluid coupler in a pipe or pipe connection. The shape is similar to the 90 degree elbow used for. Depending on the specific interferer present in the analite sample, some interferer species can be eliminated in the presence of the loosely curved portion, so to enhance the removal of the interfering species, place a loosely curved portion in the discharge chamber. It may be desirable to include it. Analite ions are carried by the fluidized plasma gas and can exit the chamber through outlet 355. In some embodiments, the inner diameter of the first region 352 and the inner diameter of the second region 354 may be the same. In other embodiments, the average inner diameter of the first region 352 is smaller than the average inner diameter of the second region 354. In yet another example, the average inner diameter of the first region 352 is larger than the average inner diameter of the second region 354. The inner diameter of each of the regions 352 and 354 does not have to be constant along the length of each region, but may be changed as needed. The materials present in the first region 352 and the second region 354 may also be the same or different. The overall shape of regions 352 and 354 may also be the same or different. Moreover, the exact length or other dimensions of the gently curved area may not be uniform. Although not shown, one or more electrodes can be used in the chamber 350, for example, a voltage is supplied to the electrodes, the voltage is utilized in the chamber 350, and a plasma discharge occurs within a portion of the chamber 350. Can be maintained. The chamber 350 may be conductive or non-conductive, depending on the other components used with the chamber 350. When the electrodes are used in the chamber 350, the electrodes are usually placed adjacent to or near the inlet of the first region 352, but this placement is not required. The exact angle at which the gently curved portion is bent may vary, for example, from about 60 degrees to about 90 degrees.

In some embodiments, the discharge chamber or discharge tube may include multiple bends. By including multiple bends, for example, the removal of interfering species such as semi-stable atoms, free electrons and photons allows the Analite molecule to leave the discharge chamber or discharge tube substantially free of these interfering species. Can be improved to go. Referring to FIG. 4A, an inlet 411, a first region 412, a first curved portion 413, and a second region 414 coupled to the first region 412 via the first curved portion 413, A discharge chamber or discharge tube 410 comprising a second curved portion 415 and a third region 416 coupled to a second region 414 via a second curved portion 415 is shown. The third region 416 comprises an exit 417. The curved portions 413 and 415 shown in FIG. 4A are both shown to be gentle curved portions, but one sharp curved portion and one gentle curved portion depending on the specific interference species that may be present. Or it may be desirable to include two sharp bends. Further, the total lengths of the curved portions 413 and 415 do not have to be the same, and it may be desirable to lengthen the curved portion 415 on the downstream side in order to further enhance the removal of the interfering species. Similarly, it may be desirable to increase the overall inner diameter of the second bend 415 to alter the pressure flow at its end of the discharge chamber 410. For example, by increasing the diameter of the second bend 415 and the third region 416, the gas flow and gas pressure in the chamber 410 can be altered to facilitate laminar flow or some other type of desired flow. You may. Although not shown, one or more electrodes can be used in chamber 410, for example, a voltage is supplied to the electrodes, the voltage is utilized in chamber 410, and a plasma discharge occurs within a portion of chamber 410. Can be maintained. The chamber 410 may be conductive or non-conductive, depending on the other components used with the chamber 410. When the electrodes are used in the chamber 410, the electrodes are usually placed adjacent to or near the inlet 411 of the first region 412, but this placement is not required.

In certain embodiments, the discharge tube or discharge chamber may include three or more bends. Referring to FIG. 4B, an inlet 451, a first region 452, a first curved portion 453, and a second region 454 coupled to a first region 452 via a first curved portion 453, Through the second curved portion 455, the third region 456 coupled to the second region 454 via the second curved portion 455, the third curved portion 457, and the third curved portion 457. A discharge chamber or discharge tube 450 with a fourth region 458 coupled to a third region 456 is shown. The fourth region 458 comprises an exit 459. Although the curved portions 455 and 457 shown in FIG. 4B are shown to be gently curved portions, it may be desirable to include a plurality of sharply curved portions depending on the specific interference species that may be present. Further, the total lengths of the curved portions 453, 455, and 457 do not have to be the same, and it may be desirable to lengthen the curved portion 457 on the downstream side in order to further enhance the removal of the interfering species. Similarly, it may be desirable to increase the overall inner diameter of the third bend 457 to alter the pressure flow at its end of the discharge chamber 450. For example, by increasing the diameter of the third bend 457 and the fourth region 458, the gas flow and gas pressure in the chamber 450 is altered to facilitate laminar flow or some other type of desired flow. You may. Although not shown, one or more electrodes can be used in the chamber 450, for example, a voltage is supplied to the electrodes, the voltage is utilized in the chamber 450, and a plasma discharge occurs within a portion of the chamber 450. Can be maintained. The chamber 450 may be conductive or non-conductive, depending on the other components used with the chamber 450. When the electrodes are used in the chamber 450, the electrodes are usually placed adjacent to or near the inlet 451 of the first region 452, but this placement is not required.

In certain embodiments, the discharge chamber or discharge tube may include two or more bends in different orientations. By including multiple curved parts with different orientations, the removal of interfering species such as semi-stable atoms, free electrons and photons can be achieved in the discharge chamber or discharge with the analog molecules substantially free of these interfering species. Reinforcement can be realized to leave the tube. Referring to FIG. 4C, an inlet 471, a first region 472, a first curved portion 473, and a second region 474 coupled to a first region 472 via a first curved portion 473, A second curved portion 475, a third region 476 coupled to the second region 474 via the second curved portion 475, and a fourth region coupled to the third region 476 via the curved portion 477. A discharge chamber or discharge tube 470 with a region of 478 is shown. The fourth region 478 comprises an exit 479. The curved portions 473, 475, and 477 shown in FIG. 4C are all shown to be gently curved portions, but one sharply curved portion and two loosely curved portions are used depending on the specific interference species that may be present. It may be desirable to include a bend or two sharp bends. Further, the total lengths of the curved portions 473, 475, and 477 do not have to be the same, and it may be desirable to lengthen the curved portion 477 on the downstream side in order to further enhance the removal of the interfering species. Similarly, it may be desirable to increase the overall inner diameter of the bend 477 to alter the pressure flow at its end of the discharge chamber 470. For example, by increasing the diameter of the third curved portion 477 and the third region 476 and the fourth region 478, the gas flow and gas pressure in the chamber 470 can be changed to laminar flow or some other kind. The desired flow may be promoted. In this explanatory view, the curved portion 473 can be regarded as a curved portion of +90 degrees, and the curved portion 475 can be regarded as a curved portion of −90 degrees. By changing the direction of the gas flow according to the different orientations of the bends 473 and 475, the collision of the interfering species with the walls of the chamber 470 can be enhanced, thereby eliminating these interfering species. Can work. Analite ions can be mixed into the central gas stream, which moves below chamber 470 and exits through outlet 479. Although not shown, one or more electrodes can be used in chamber 470, for example, a voltage is supplied to the electrodes, the voltage is utilized in chamber 470, and a plasma discharge occurs within a portion of chamber 470. Can be maintained. The chamber 470 may be conductive or non-conductive, depending on the other components used with the chamber 470. When the electrodes are used in chamber 470, the electrodes are typically placed adjacent to or near the inlet 471 of the first region 472, but this placement is not required.

In some embodiments, the discharge chambers described herein may include multiple inlets. Referring to FIG. 5A, the discharge chamber 510 includes a first inlet 511, a second inlet 513, and an outlet 515. In some embodiments, inlets 511 and 513 may be fluidly coupled to different plasma gases so that only one plasma gas can enter chamber 510 at any time. In another example, inlets 511 and 513 can be used to simultaneously introduce two different plasma gases into chamber 510. The pressure and flow rate of each plasma gas may be the same or different, and in-line mixing of the two gases can be achieved within the chamber 510.

In other configurations, the sample may be introduced through one of the inlets 511 and 513 and the plasma gas may be introduced into the other of the inlets 511 and 513. In the configuration of FIG. 5A, the sample is introduced into the chamber coaxially with the plasma gas through the inlets 511 and 513. However, if desired, one of the plasma gas and the sample may be introduced into the chamber non-coaxially. For example, with reference to FIG. 5B, a chamber 550 with a first inlet 551, a second inlet 553, and an outlet 555 is shown. The second entrance 553 is approximately orthogonal to the first entrance 551. If desired, two different plasma gases may be introduced through inlets 551 and 555, and another inlet may be present to introduce the sample into chamber 550. Additional inlets for the sample may be coaxial with inlets 551 or 553, or may be located at different angles with respect to inlets 551 and 553.

In some embodiments, the discharge chamber may include multiple outlets. With reference to FIG. 5C, a discharge chamber 570 with an inlet 572, a first outlet 574, and a second outlet 576 is shown. The first outlet 574 and the second outlet 576 can be located in many different positions, and one or more of the outlets 574, 576 can be blocked as needed, so that the ions can block the outlet 574, Exit only from one of the 576.

In certain embodiments, the discharge chambers described herein may have variable inner diameters at various parts of the discharge chamber. Referring to FIG. 6A, the discharge chamber 605 includes an inlet 606 and an outlet 607. The inner diameter of the discharge chamber 605 increases from the inlet 606 to the outlet 607. However, if necessary, the average inner diameter may be reduced from the inlet 606 to the outlet 607. The change in the size of the inner diameter from one end of the chamber 605 to the other end of the chamber 605 need not be linear or conical, but may be bell-shaped instead, or other forms and optionally. It may take a shape.

In some embodiments, the inner diameter of the discharge chamber may be variable at different parts of the discharge chamber. Referring to FIG. 6B, the discharge chamber 610 includes an inlet 611 and an outlet 612. The inner diameter of the chamber 610 increases from the inlet 611 toward the center of the chamber 610 and then decreases towards the outlet 612 of the chamber 610. The change in inner diameter need not be linear or conical and may not be the same on each side of the chamber 610. For example, referring to FIG. 6C, the distance d1 of the chamber 620 from the central longitudinal axis 625 may be substantially constant along the longitudinal direction of the chamber 620, the opposite of the central longitudinal axis 625 to the chamber 620. The lateral distance d2 may vary along the longitudinal direction of chamber 620.

In certain embodiments, the discharge chamber with one or more bends may also have a variable inner diameter along the longitudinal direction of the chamber. With reference to FIG. 6D, the discharge chamber 630 has a first region 631 (which may include an inlet), a curved portion 632, and a second region 633 (which may be coupled to the first region 631 via the curved portion 632). Includes an exit). The inner diameter of the second region 633 is (on average) larger than the inner diameter of the first region 631. By increasing the inner diameter from the first region 631 to the second region 633, the flow characteristics of the chamber 630 are adjusted so that certain interfering species are removed and they virtually never leave the chamber 630. It can be changed. In another example, the inner diameter may be reduced from the inlet end to the outlet end of the discharge chamber. Chamber 630 also comprises a third region 635 coupled to a second region 633 via a bend 634. The inner diameter of the third region 635 can be made larger than the inner diameter of the second region 633 so as to change the flow characteristics of the discharge chamber 630.

In one particular configuration, two or more of the discharge chambers may be fluidly coupled to each other to allow the transfer of analytical ions from one chamber to another. For example, with reference to FIG. 7A, the first discharge chamber 710 is shown to be coupled to the second discharge chamber 720 via the interface 715. Samples and / or plasma gas can enter the assembly through one or more inlets of chamber 710. If desired, the interface 715 may be omitted so that the end of the discharge chamber 710 is frictionally fitted to the upstream end of the chamber 720, for example by inserting the first chamber 710 into the second chamber 720. May be resized and placed. Friction fits may be adequately tight to hold the two chambers together, or at least fasteners, adhesives, fittings or fittings to hold the two chambers 710, 720 to each other during analysis. May be used. In some examples, the discharge chamber can be assembled and arranged as a module that combines with another modular discharge chamber to allow the user to choose the overall length and nature of the combined assembly. The two chambers 710, 720 are shown to be substantially the same in FIG. 7A, but this feature is not essential. With reference to FIG. 7B, the straight discharge chamber 730 is shown to be coupled to the curved discharge chamber 740. Samples and / or plasma gas can enter the assembly through one or more inlets of chamber 730. If desired, the orientation may be reversed so that the sample and / or plasma gas enters chamber 740. The orientation of the combined assemblies also need not be the same.

In some embodiments, two or more discharge chambers arranged in parallel may be coupled to the inlet of the mass spectrometer. With reference to FIG. 7C, a first discharge chamber 770 and a second discharge chamber 772 are shown. Each of the chambers 770 and 772 is fluidly coupled to the upstream sample introduction device 765. The sample introduction device 765 may be configured to direct the analysts to one or both of the chambers 770, 772. For example, the sample introduction device may be provided with a solenoid valve capable of fluidly coupling and separating the sample flow in one of the chambers 770 and 772, or the sample flow may be divided and supplied to both chambers. good. The chambers 770, 772 can be configured differently so that different analyte species can be supplied to one of the different chambers. For example, if it is believed that ionization using plasma discharge maintained in a straight chamber will result in few interfering species, it may be desirable to supply the first analyze to the straight chamber. For the second analyst, supply the second analyst to the curved chamber if more interfering species are generated and it is considered necessary to remove any ions before they emerge from the chamber. May be desirable. Chambers 770, 772 may be fluidly coupled to downstream components, eg, mass spectrometers separately, or to downstream components via a common interface (not shown). You may. Although not shown, three, four, or more chambers may be arranged in parallel. Further, any one parallel chamber may include a single discharge chamber or two or more discharge chambers coupled to each other.

In some configurations where two or more discharge chambers are fluidly coupled to each other, each of the discharge chambers may be configured to maintain its own plasma discharge, or only one of the discharge chambers. It may be configured to maintain plasma discharge. In some embodiments, the two discharge chambers may use the same plasma gas, but each of the chambers (or one or more electrodes in each chamber) may be supplied with a different voltage. In other embodiments, the two discharge chambers may use different plasma gases, and the chambers (or one or more electrodes of the chamber) may be supplied with similar voltages. In some embodiments, the two discharge chambers may use different plasma gases, and each chamber (or one or more electrodes in each chamber) may be supplied with a different voltage. The use of two discharge chambers arranged in series allows the operation of one or two plasmas depending on the desired analyze sample. In some embodiments, the upstream discharge chamber (relative to the inlet position) can be used to maintain the plasma discharge, and the downstream discharge chamber is for removing more interfering species. Can be used to provide additional length for. In another example, the downstream discharge chamber can be used to maintain the plasma discharge, and the upstream discharge chamber can be used to mix the sample with gas or other species. For example, different gases can be introduced with the sample into the upstream chamber to allow the mixture to reach a plasma discharge maintained in the downstream chamber after the gas and sample have been mixed.

In certain embodiments, the actual plasma gas selected for use with the power dissipation described herein may vary. Plasma gases can be, for example, helium, neon, argon, krypton, xenone, nitrogen, nitric oxide, ammonia, oxygen, ozone, air, compressed air, hydrogen, methane, carbon monoxide, carbon dioxide, and nitrogen dioxide. .. Other gases are also possible. In some embodiments, two or more of these gases can be used in the gas mixture to maintain a plasma discharge in the discharge chamber. The gas composition can be varied with the various Analite species in the sample, if desired. For example, when the first analyst is introduced into the discharge chamber, a first gas may be used to maintain the plasma discharge. Once the first announcer is ionized out of the chamber, a second gas may then be introduced to maintain the plasma discharge when the second announcer is introduced into the discharge chamber. By selecting a particular plasma gas, more selective ionization of each announcer in the sample can be achieved.

In some embodiments, the flow rate of the plasma gas may be selected to provide the desired pressure into the discharge chamber. For example, the plasma discharge can be maintained at a pressure of about ^{10-3 torr to about 100 torr.} The pressure does not have to be constant during the operation of the plasma discharge. For example, for certain analysts, it may be desirable to operate the plasma discharge at a higher or lower pressure. In some embodiments, although not desired to be limited by these descriptive flow rates, the gas flow rate to the discharge chamber is, for example, about 500 standard cubic centimeters (sccm) per minute, or less than 500 sccm, or less than 150 sccm. , Or can be less than 100 sccm. In many cases, the gas flow rate used in the discharge chambers described herein is significantly lower compared to traditional inductively coupled plasmas operating at argon flow rates of 15 liters / minute and above, thereby saving costs. And can result in more efficient operation of the device. It is an important attribute to be able to maintain the plasma discharge using such a low flow rate. If desired, the discharge chamber can also be heated or cooled using gas or an external heating device or cooler. For example, a heater or cooler may be thermally coupled to the discharge chamber to control the temperature of the discharge chamber. The heating device or cooler does not need to be thermally coupled to the entire chamber, but for example, it is thermally coupled to the areas adjacent to the plasma discharge, reducing the possibility of the chamber melting in these areas. can do.

In some embodiments, the discharge chambers described herein may include one or more conductive materials, or one or more areas containing conductive materials. As mentioned in many examples, the entire chamber does not have to be conductive, and the chamber can be conductive using electrodes, coatings, or by including a conductive material in a particular area. In some embodiments, the conductive coating may be present at the inlet edge and in the area downstream of the inlet edge. The inlet end can be electrically coupled to the power supply and the downstream region can be electrically coupled to the power supply or ground. If desired, the entire chamber may be made of a conductive material. Conductive materials can be installed and placed in the chamber in a variety of ways, but regardless, conductive materials are stainless steel, nickel-chromium alloys, nickel-chromium molybdenum alloys, titanium, titanium alloys, lanthanoids, lanthanoid alloys. , Actinides, actinide alloys, and one or more of combinations thereof. Although these materials are not essential, high temperature metallic materials can extend their lifespan and reduce the need for maintenance.

In some examples where the discharge chamber contains metal, the metal can make the chamber optically opaque. If necessary, an optical window can be provided in the discharge chamber so that the plasma discharge can be observed. With reference to FIG. 8, the optical window 820 is shown to be near the inlet end 812 of the discharge chamber 810. The optical window may include quartz or other optically transparent material to allow the user to determine if the plasma discharge is maintained within the chamber 810. As a safety mechanism, the device can be provided with an optical sensor for receiving light emission due to plasma discharge. For example, when the plasma discharge disappears, there may be an optical sensor, which can be configured to drop the voltage supplied to the chamber (or the electrodes used in the chamber) as a safety mechanism. In addition, the sensor may stop the flow of plasma gas to save gas. At the time of plasma ignition, there may be a time window in which the optical sensor is disabled to allow gas flow and plasma ignition before the safety sensor initiates termination of voltage and / or plasma gas flow. .. In other examples, optical windows may not be provided and the current delivered to the chamber (or the electrodes used in the chamber) is monitored to determine if the plasma discharge is maintained or extinguished. You may.

In some configurations, the actual voltage delivered to the conductive regions or electrodes used in the discharge chambers described herein may also vary. As described herein, this voltage can vary with different analysts and / or different plasma gases. The supply voltage can be supplied from a DC source, an AC source, or a radio frequency source. When a DC voltage is used, the voltage can vary from about 10 volts to about 5000 volts. The DC voltage may be positive or negative, and may be, for example, +/- 10 volts to +/- 5000 volts. If an alternating voltage is available, this alternating current can vary, for example, from about 20 volts to about 3000 volts. The AC voltage may be positive or negative, for example, +/- 20 volts to +/- 3000 volts. When radio frequency currents are used, the radio frequency range can be from about 100 Hz to about 10 MHz. The voltage values described herein are provided for illustration purposes only and are not intended to limit the actual voltage values that can be used. Different types of current can be used for different analysts, if desired. For example, when the first analyst is introduced into the discharge chamber, an alternating current can be used to maintain the plasma discharge to ionize the first analyst. When the second announcer is introduced into the discharge chamber, direct current can be used to maintain the plasma discharge to ionize the second announcer. In an embodiment in which two or more discharge chambers are coupled to each other, one of the discharge chambers may use a first type of voltage to maintain a first plasma discharge, the other discharge chamber. A different type of voltage may be used to maintain the second plasma discharge.

In certain embodiments, the discharge chambers described herein can be used in systems with one or more other components. For example, the discharge chamber may fluidly bind to an upstream component capable of supplying the announcer to the inlet of the discharge chamber and / or supply the ion to the downstream component for analysis or further utilization. In order to do so, it can be fluidly coupled to the downstream components. With reference to FIG. 9A, the discharge chamber 930 is shown to be fluidly coupled to the gas chromatography system. The gas chromatography system comprises an injector 905 fluidly coupled to a column 910 placed in an oven 915. The injector 905 and / or column 910 is also fluidly coupled to a mobile phase 925, a gas, which can be used with the stationary phase of column 910 to separate two or more analysts in the introduced sample. There is. As the individual analysts elute from column 910, they can be fed to the inlet of the discharge chamber 930 for ionization. As shown in FIG. 9A, the inlet for introducing the sample is different from the inlet 932 for introducing the plasma gas, but if necessary, the sample inlet may be the same. The column 910 is shown to be directly coupled to the inlet of the discharge chamber 930, but one or more transfer lines, interfaces, etc. may be used instead. For example, a transfer line 940 may be used to fluidly couple the column 910 to the inlet of the discharge chamber 930. The transfer line 940 may be heated (if required or on request) to keep the analyte in the gas phase. Additional components, such as interfaces, splitters, photodetector cells, enrichment chambers, filters, and the like, may also be present between column 910 and chamber 930.

In some embodiments, the discharge chamber can be fluidly coupled to a liquid chromatography (LC) system. Referring to FIG. 9B, the LC system comprises an injector 955 fluidly coupled to the column 960 via one or more pumps 957. The injector 955 and / or column 960 is also fluidly coupled to a mobile phase, i.e., a liquid and one or more pumps 957 that can be used to pressurize the LC system. Column 960 generally contains a stationary phase selected to separate two or more analysts in the introduced sample. As the individual analysts elute from column 960, they can be fed to the inlet of the discharge chamber 970 for ionization. The column 960 is shown to be directly coupled to the inlet of the discharge chamber 970, but one or more transfer lines, interfaces, etc. may be used instead. For example, a flow splitter may be used if desired. Additional components, such as interfaces, splitters, photodetector cells, enrichment chambers, filters, and the like, may also be present between column 960 and chamber 970. As shown in FIG. 9B, the inlet for introducing the sample from the LC system is different from the inlet 972 for introducing the plasma gas, but they may be the same, if desired.

In some embodiments, the discharge chamber may be inside the mass spectrometer. For example, the discharge chambers disclosed herein may also be used inside or with a mass spectrometer. Specifically, the mass spectrometer may include one or more discharge chambers that are directly coupled to the inlet of the mass spectrometer, or one or more discharge chambers that are spatially separated from the inlet of the mass spectrometer. May include. A descriptive MS device is shown in FIG. The MS device 1000 includes a sample introduction device 1010, a discharge chamber 1015, a mass spectrometer 1020, a detection device 1030, a processor 1040, and an optional display (not shown). The mass spectrometer 1020 and the detection device 1030 may operate under reduced pressure using one or more vacuum pumps and / or vacuum pumping stages, as described in more detail below. The sample introduction device 1010 may be a GC system, LC system, nebulizer, aerozoizer, spray nozzle or spray head, or other device capable of supplying a gas or liquid sample to the discharge chamber 1015. If a solid sample is used, the sample introduction device 1010 may include a direct sample analysis (DSA) device, or other device, capable of introducing the analog species from the solid sample. The discharge chamber 1015 can be any of those described herein, or any other suitable discharge chamber. The mass spectrometer 1020 can generally take many forms depending on the properties of the sample, the desired resolution, and the like, and an exemplary mass spectrometer will be described later. The detection device 1030 may be any suitable detection device that can be used with existing mass spectrometers, such as a photomultiplier tube, Faraday cup, coated photosensitive plate, scintillation detector, etc., benefiting from the present disclosure. It may be another suitable device that will be selected by those skilled in the art. Processor 1040 generally includes a microprocessor and / or computer and suitable software for the analysis of samples installed in the MS device 1000. If desired, one or more databases may be accessed by processor 1040 to determine the chemical identity of the species introduced into the MS device 1000. Also, other suitable additional devices well known in the art, such as, but not limited to, PerkinElmer Health Sciences, Inc. It may be used with the MS device 1000 including an autosampler such as the AS-90plus autosampler and the AS-93plus autosampler commercially available from.

In certain embodiments, the mass spectrometer 1020 of the MS device 1000 can take many forms, depending on the desired resolution and the nature of the introduced sample. In certain embodiments, the mass spectrometer is a scanning mass spectrometer, a magnetic sector analyzer (eg, single-focused and double-focused MS devices) capable of separating chemical species with different mass-to-charge ratios. (Used), quadrupole mass spectrometers, ion trap analyzers (eg cyclotrons, quadrupole ion traps), flight time analyzers (eg matrix-assisted laser desorption / ionization flight time analyzers), and others. A suitable mass spectrometer. As will be described in more detail below, the mass spectrometer has two or more different devices arranged in series, eg, two, to select and / or identify the ions received from the discharge chamber 1015. MS / MS device, or triple quadrupole device may be provided.

In certain other embodiments, the discharge chambers disclosed herein may be used in conjunction with existing ionization methods used in mass spectrometry. For example, it is possible to assemble an MS instrument having a dual source in which one of the sources is the discharge chamber described herein and the other source is another ionization source. This other ionization source is, for example, an electron impact source, a chemical ionization source, an electric field ionization source, for example, high-speed atomic impact, electric field desorption, laser desorption, plasma desorption, thermal desorption, electrohydrodynamic ionization / desorption. It may be a desorption source such as a source configured for desorption and the like, a heat spray or electrospray ionization source, or other type of ionization source. By including two different ionization sources in a single instrument, the user can select a particular ionization method that can be used.

According to certain other embodiments, the MS system disclosed herein can be hyphenated with one or more other analytical techniques. For example, the MS system can be hyphenated into one or more devices for performing liquid chromatography, gas chromatography, capillary electrophoresis, and other suitable separation techniques. When coupling an MS device to a gas chromatograph, it may be desirable to include an appropriate interface for introducing samples from the gas chromatograph into the MS device, such as traps, jet separators, and the like. When coupling an MS device to a liquid chromatograph, it may also be desirable to include an appropriate interface to compensate for the volume differences used in liquid chromatography and mass spectrometry. For example, a split interface may be used such that only a small amount of sample exiting the liquid chromatograph is introduced into the MS device. Samples leaving the liquid chromatograph may be deposited in a suitable wire, cup, or chamber for transport to the discharge chamber of the MS device. In certain embodiments, the liquid chromatograph may include a thermospray configured to vaporize and aerosolize the sample as it passes through the heated capillaries. Other suitable devices for introducing liquid samples from liquid chromatographs into MS devices or other detection devices will be readily selected by one of ordinary skill in the art to benefit from the present disclosure.

In certain embodiments, for tandem mass spectrometry, the MS device, including the discharge chamber, is hyphenated to at least one other MS device, which may or may not include its own discharge chamber. obtain. For example, one MS device may include a first type mass spectrometer, and the second MS device may include a mass spectrometer different from or similar to the first MS device. In other examples, the first MS device can act to isolate the molecular ions and the second MS device can act to fragment / detect the isolated molecular ions. It is within the ability of one of ordinary skill in the art to design a hyphenated MS / MS device, at least one of which includes a discharge chamber. In some embodiments, the MS device may comprise two or more quadrupoles that may be configured the same or differently. For example, the triple quadrupole assembly shown in the examples attached herein can be used to select ions from an ion beam exiting the discharge chamber.

In certain embodiments, the methods and systems herein can be part of a system or device, or can be present on related devices used in the device, such as computers, laptops, mobile devices, and the like. It may be equipped with a processor or may be used. For example, the processor can be used to control the supply voltage to the discharge chamber and any electrode, control a mass spectrometer, and / or be used by a detector. Such a process may be performed automatically by the processor without the intervention of the user, or the user may enter parameters via the user interface. For example, the processor can use signal strength and fragment peaks with one or more calibration curves to determine identity and how much each molecule is present in the sample. In certain configurations, the processor provides, for example, a microprocessor and / or suitable software for operating the system to control a sample introduction device, an ionization device, a mass analyzer, a detector, and the like. It may be present in one or more computer systems and / or common hardware circuits, including. In some embodiments, the detection device itself may have its own processor, operating system, and other features to allow detection of various molecules. The processor may be integrated with the system or may be present on one or more accessory boards, printed circuit boards, or computers that are electrically coupled to the components of the system. Processors generally receive data from other components of the system and are electrically coupled to one or more memory units so that various system parameters can be adjusted as needed or desired. Processors are part of general purpose computers based on Unix®, Intel PENTIUM® type processors, Motorola PowerPC, Sun UltraSPARC, Hewlett-Packard PA-RISC processors, or any other type of processor. There may be. According to various embodiments of the present technology, one or more computer systems of any type may be used. Further, the system may be connected to a single computer or distributed among multiple computers connected by a communication network. It should be understood that other functions, including network communication, can be performed and the technology is not limited to having any particular function or set of functions. Various aspects can be implemented as dedicated software running on a general purpose computer system. A computer system may include a processor attached to one or more memory devices, such as a disk drive, memory, or other device for storing data. The memory is typically used to store programs, calibration curves, and data values during the operation of any device, including the discharge chamber and the discharge chamber. Computer system components include one or more buses (eg, between components built into the same machine) and / or networks (eg, between components that reside on separate, distributed machines). Can be coupled by the interconnecting device that gets. Interconnect devices provide communications (eg, signals, data, instructions) to be exchanged between system components. Computer systems can generally receive and / or issue commands within a processing time of, for example, a few milliseconds, a few microseconds or less, to allow rapid control of the system. For example, computer control for controlling sample introduction, plasma gas flow and pressure, detector parameters, etc. may be implemented. The processor is typically electrically coupled to a power source, which may be, for example, a DC source, an AC source, a battery, a fuel cell, or another power source, or a combination of power sources. The power supply may be shared by other components of the system. The system also includes one or more input devices such as keyboards, mice, trackballs, microphones, touch screens, manual switches (eg override switches), and one or more output devices such as printing devices, display screens. A speaker may be included. In addition, the system may include one or more communication interfaces (in addition to or as an alternative to interconnect devices) that connect the computer system to the communication network. The system may also include suitable circuits for converting signals received from various electrical devices present in the system. Such circuits may be present on a printed circuit board, or via suitable interfaces such as serial ATA interfaces, ISA interfaces, PCI interfaces, or the like, or one or more wireless interfaces. For example, it may reside on a separate board or device that is electrically coupled to the printed circuit board via Bluetooth, Wi-Fi, short range radio communications, or other radio protocols and / or radio interfaces.

In certain embodiments, the storage system used in the systems described herein is typically a computer-readable medium and write-once medium in which software code may be stored, which may be used by a program to be executed by the processor. Includes possible non-volatile recording media, or media or information stored in the media to be processed by the program. The medium may be, for example, a hard disk, a solid state drive, or a flash memory. Programs or instructions executed by the processor can be located locally or remotely and can be retrieved by the processor via interconnection mechanisms, communication networks, or other means as needed. Normally, during operation, the processor causes the data to be read from the non-volatile recording medium to another memory that allows the processor to access information faster than the medium. This memory is generally volatile random access memory such as dynamic random access memory (DRAM) or static memory (SRAM). This memory can be installed in the storage system or in the memory system. The processor generally processes the data in the integrated circuit memory and then copies the data to the medium after the processing is complete. Various mechanisms for managing data movement between media and integrated circuit memory elements are known, and the present technology is not limited thereto. Further, the present technology is not limited to a specific memory system or storage system. In certain embodiments, the system may also include specially programmed dedicated hardware, such as an application specific integrated circuit (ASIC) or a field programmable gate array (FPGA). Aspects of the art may be implemented in software, hardware, or firmware, or any combination thereof. Further, such methods, actions, systems, system elements, and components thereof may be implemented as part of the above system or as independent components. It should be understood that the particular system is described as, by way of example, as one type of system in which various aspects of the technique can be implemented, but the embodiments are not limited to implementation on the described system. Various aspects can be implemented on one or more systems with different architectures or components. The system may include a general purpose computer system that can be programmed using a high level computer programming language. The system may also be implemented using specially programmed special purpose hardware. In this system, the processor is generally a commercially available processor, such as the well-known Pentium® class processor available from Intel Corporation. Many other processors are commercially available. Such processors are usually available, for example, from Windows 95, Windows 98, Windows NT, Windows 2000 (Windows ME), Windows XP, Windows XP, Windows Vista, Windows 7, Windows 7 and Windows Systems. MAC OS X available from, for example, Snow Leopard, Lion, Mountain Lion, or other versions, Solaris operating system available from Sun Windows, or UNIX® or Linux® available from various sources. (Trademark) Runs an operating system that can be an operating system. Many other operating systems may be used, and in certain embodiments, a command or a simple set of instructions may act as the operating system. In addition, the processor can be designed as a quantum processor designed to perform one or more functions using one or more qubits.

In a particular example, the processor and operating system can both define a platform on which application programs can be written in a high-level programming language. It should be understood that the technology is not limited to any particular system platform, processor, operating system, or network. Also, given the advantages of the present disclosure, it will be apparent to those skilled in the art that the art is not limited to any particular programming language or computer system. In addition, it should be understood that other suitable programming languages and other suitable systems can be used. In certain examples, the hardware or software may be configured to build a cognitive architecture, neural network, or other suitable implementation. If desired, one or more parts of the computer system may be distributed across the one or more computer systems coupled to the communication network. These computer systems can also be general purpose computer systems. For example, various aspects are configured to provide a service (eg, a server) to one or more client computers, or to perform an overall task as part of a distributed system. It may be distributed among computer systems. For example, different aspects may be performed in a client-server system or a multi-layer system that includes components distributed among one or more server systems that perform different functions in different embodiments. These components communicate over a communication network (eg, the Internet) using a communication protocol (eg, TCP / IP), executable code, intermediate code (eg, IL), or interpreted code (eg, eg). , Java). It should also be understood that the technology is not limited to running in any particular system or group of systems. It should also be understood that the technology is not limited to any particular distributed architecture, network, or communication protocol.

In some cases, various embodiments are object-oriented programming languages such as SQL, SmallTalk, Basic, Java, Javascript, PHP, C ++, Ada, Python, iOS / Swift, Ruby on Rails, or C # (Sea Sharp). May be programmed using. Other object-oriented programming languages can also be used. Alternatively, a functional programming language, a script programming language, and / or a logical programming language may be used. Various configurations can be implemented in an unprogrammed environment (eg, an HTML that renders aspects of a graphical user interface (GUI) or performs other functions when viewed in a browser program window. , XML, or other document). Certain configurations may be implemented as programmed or unprogrammed elements, or any combination thereof. In some examples, the system may be a mobile device, tablet, laptop computer, or other portable device that communicates over a wired or wireless interface and allows remote operation of the system as needed. It may have a remote interface as it exists.

In certain embodiments, the processor also includes a database of information about molecules, their fragmentation patterns, and the like, which may include molecular weight, mass-to-charge ratio, and other common information. You can access them. Instructions stored in memory can execute software modules or control routines of the system, thereby providing a substantially controllable model of the system. The processor uses the information accessed from the database in conjunction with one or more software modules running on the processor to control parameters or values of various components of the system, such as different plasma gas flows, different. The electrode voltage, various mass analyzer parameters, etc. can be determined. The processor can perform active control of the system using an input interface for receiving control instructions and an output interface linked to various system components of the system. For example, the processor can control the detection device, sample introduction device, discharge chamber, electrodes, and other components of the system.

In certain embodiments, the discharge chamber can be used in a manner that comprises ionizing the analysts by introducing them into a plasma discharge maintained within a discharge chamber comprising a first electrode. The discharge chamber can be configured similarly to any of those described herein, eg, one having at least one inlet and at least one outlet. Plasma discharge can be maintained in the discharge chamber by supplying a voltage to the first electrode in the presence of plasma gas introduced into the discharge chamber through at least one inlet of the discharge chamber. For example, a DC voltage of about 10 to about 5000 volts supplied to the first electrode can be used to maintain a plasma discharge in the discharge chamber. An AC voltage of about 20 to about 3000 volts supplied to the first electrode can be used to maintain a plasma discharge in the discharge chamber. Radio frequency current may be supplied to the first electrode in the radio frequency range of about 100 Hz to about 10 MHz to maintain plasma discharge in the discharge chamber. The actual gas pressure used can fluctuate, and descriptive pressures include pressures that can maintain the plasma discharge in the discharge chamber at a pressure suitable to avoid extinction of the plasma discharge. Not limited to these. In a non-limiting example, ^{a pressure of about 10 -3 to} 100 torr may be used. In another non-limiting example, a plasma gas flow rate of 500 sccm or less can be used to maintain the plasma discharge. As described herein, the discharge tube can be configured in many different ways, with a first area adjacent to at least one inlet, a third area adjacent to at least one outlet, and A second area between the first area and the third area may be provided. If necessary, the average inner diameter of the third area is larger than the average inner diameter of the second area.

In some embodiments, the plasma discharge is such that it promotes the production of the parental ananalytes of the ionized analysts and allows the quantification of the analysts using the mass vs. charge peak intensity of the parental analysts. You can select the parameters used to maintain. For example, the softer ionization provided by plasma discharge may be used, for example, to increase the amount of precursor ions produced compared to the amount of precursor ions produced using electron ionization. good. The current supplied to the first electrode may be monitored to determine if the plasma discharge is maintained in the discharge chamber. As described herein, two or more plasma gases, two or more chambers or two or more different voltages can be used to maintain a plasma discharge. The parameters may be changed between different analysts to provide selective ionization of different analysts.

In some embodiments, the method comprises providing a discharge chamber configured to maintain plasma discharge within the discharge chamber. The discharge chamber can be configured to electrically couple to at least one electrode that is configured to couple to a power source. The discharge chamber may include at least one inlet, at least one outlet, and at least one optional bend between at least one inlet and at least one outlet. The discharge chamber can be configured to maintain plasma discharge within the discharge chamber using the voltage supplied to at least one electrode.

In some examples, the method of quantifying the analysts in the sample is the plasma generated in the discharge chamber by using any suitable plasma gas flow rate, for example, a plasma gas flow rate of 500 sccm or less in one example. After introducing the analite into the discharge, the plasma gas involves measuring the peak intensity of the parent analyte ion produced from the ionization of the analite, using the plasma discharge generated to generate the parental analyte ion. Selected to increase production.

In another embodiment, the method of ionizing the analytes to increase the production of parental analyte ions uses the plasma gas supplied to the discharge chamber and the voltage supplied to the discharge chamber to use the discharge chamber. The plasma discharge is maintained in the discharge chamber using any suitable plasma gas flow rate, such as, for example, a plasma gas stream of 500 sccm or less, comprising introducing an analyzer into the plasma discharge maintained therein. The plasma discharge contains an average temperature of about 2000 Kelvin or less.

In some embodiments, the plasma discharge comprises an average temperature of about 2000 kelvin or less and the plasma discharge uses the voltage supplied to the discharge chamber in the presence of plasma gas supplied at a plasma gas flow rate of 500 sccm or less. It is then maintained in the discharge chamber.

In certain embodiments, the discharge chamber may be packed into a kit with instructions for use to provide plasma discharge within the discharge chamber using a plasma discharge ionization source. For example, this manual may allow the end user to retrofit existing equipment to the discharge chamber.

Next, some specific embodiments will be described to further describe some of the novel aspects and features of the techniques described herein.

Example 1
With reference to FIG. 11, an explanatory view of the discharge chamber with the stainless steel chamber 1120 is shown. The gas chromatography (GC) inlet 1112 is fluidly coupled to the fluid transfer line 1114 to transfer the analyze from the GC system to chamber 1120. Plasma gas enters the chamber in the direction of arrow 1116. A probe containing the electrode 1118 is electrically coupled to a DC power source to supply voltage to the electrodes. Plasma gas and electrodes 1118 can be used to maintain the plasma discharge 1122 in chamber 1120. Analytes from the GC can be ionized and the analysts can exit chamber 1120 through outlet 1124 and be provided to a downstream mass spectrometer.

Example 2
With reference to FIG. 12, an explanatory view of the discharge chamber including the stainless steel chamber 1220 is shown. The gas chromatography (GC) inlet 1212 is fluidly coupled to the fluid transfer line 1214 to transfer the analyze from the GC system to the chamber 1220. The plasma gas enters the chamber in the direction of arrow 1216, passes through the fluid transfer line 1214 and enters the chamber 1220. A probe containing the electrode 1218 is electrically coupled to a DC power source to supply a voltage to the electrode. Plasma gas and electrodes 1218 can be used to maintain the plasma discharge 1222 in chamber 1220. Analytes from the GC can be ionized, which can exit chamber 1220 through outlet 1224 and be provided to a downstream mass spectrometer.

Example 3
Various plasma gases can be selected based on their ionization potential. Table 1 shows the values of various plasma gases. In Table 1, E * represents metastable energy, _trad represents radiation lifetime, and E ⁱ represents ionization energy (atomic or molecular species).
Table 1

Example 4
With reference to FIG. 13, an explanatory view of the discharge chamber 1310 coupled directly to the inlet of the mass spectrometer 1320 is shown. The outlet of the discharge chamber 1310 is directly coupled to the inlet of the first pumping stage 1322, and the outlet and the first pumping stage 1322 (denoted as M0) are fluidly coupled. The first pumping stage 1322 is fluidly coupled to the second pumping stage 1324 (denoted as M1) and the second pumping stage 1324 is fluidly coupled to the third pumping stage 1326 (denoted as M2). Combine to. Each of the pumping stages can be fluidly coupled to one or more pumps (indicated by arrows in FIG. 13) to reduce pressure in various pumping stages, but stage 1322 (denoted as M0). Does not have to be fluidly coupled to any pump, if desired. The third pumping stage 1326 is fluidly coupled to a triple quadrupole assembly 1330 containing a first quadrupole Q1, a second quadrupole CC, and a third quadrupole Q2. The second quadrupole CC can be configured as a collision quadrupole, and the first quadrupole Q1 and the third quadrupole Q2 are configured to select ions from the incident ion beam. Can be done. A detector (not shown) can be fluidly coupled to Q2 to receive the selected ions and determine the number of ions present. The mass spectrometer 1330 need not include all the stages or components shown in FIG.

Example 5
FIG. 14 shows the mass spectrum of hexatriacontane _{(C 36} H _{74 MW = 506.9) using electron ionization.} Since there are no precursor ions in the mass spectrum, this analyze can be identified only when fragment ions are used. 15A-15C show the spectra of hexatriacontane (FIG. 15A), tetracontane (FIG. 15B) and tetratetracontane (FIG. 15C) using the electron ionization method. The major fragments of the mass spectrum are all hydrocarbon fragments, making it difficult to identify various species.

Example 6
_{The mass spectrum of hexatriacontane (C 36} H ₇₄ MW = 506.9) was obtained using the discharge tube and mass spectrometer setup shown in FIG. The voltage supplied to maintain the discharge was about -500 volts. In the scan of FIG. 16B, argon was used as the plasma gas at a flow rate of about 50 sccm. Zero air was used in the scans of FIGS. 16A and 16B. Argon was used as the collision gas to obtain the scan shown in FIG. 16B. The results are shown in FIGS. 16A and 16B. FIG. 16C includes an electron ionization scan for comparison.

Referring to FIG. 16A, Q1MS full scan ^{shows increased production of precursor ions (M +} and / or [MH] ⁺ ), while using conventional EI. , Precursor ions are rarely observed (Fig. 16C). The generated ion scan (FIG. 16B) also shows the presence of large amounts of precursor ions. By increasing the amount of precursor ions, the precursor ions can be used to identify the molecules in the sample and / or quantify the amount of molecules in the sample.

In bringing up the elements of the examples disclosed herein, the articles "a", "an", "the", and "said" are intended to mean that one or more of the elements are present. Has been done. The terms "comprising", "inclusion", and "having" are intended to be non-restrictive and there may be additional elements other than those described. Means that. Given the advantages of the present disclosure, it will be appreciated by those skilled in the art that the various components of this example can be replaced or replaced with the various components of other examples.

Specific embodiments, examples, and embodiments have been described above, but given the advantages of the present disclosure, the disclosed exemplary embodiments, examples, and embodiments may be added, replaced, modified, and modified. Will be recognized by those skilled in the art.

Claims (50)

A plasma discharge ion source with a discharge chamber
With a conductive area,
The discharge chamber is configured to maintain plasma discharge within the discharge chamber.
The discharge chamber
With at least one inlet configured to receive plasma gas,
The plasma discharge ionization source comprising at least one outlet configured to provide ionized analysts from the discharge chamber. A first electrode electrically coupled to the discharge chamber is further provided.
The plasma discharge ion source according to claim 1, wherein the first electrode is configured to be electrically coupled to a power source. The plasma discharge ionization source according to claim 1, wherein the first electrode is arranged in the at least one inlet of the discharge chamber. The plasma discharge ion source according to claim 1, further comprising a second electrode electrically coupled to the discharge chamber. At least one curved portion is further provided between the at least one inlet and the at least one outlet.
The plasma discharge ionization source according to claim 1, wherein the at least one curved portion is configured to reduce the number of semi-stable atoms and free electrons and photons exiting the discharge chamber through the at least one outlet. .. The plasma discharge ionization source according to claim 5, wherein the at least one curved portion is configured as a curved portion of about 90 degrees. The plasma discharge ionization source according to claim 5, further comprising a second curved portion located upstream of the at least one curved portion or downstream of the at least one curved portion. The plasma discharge ion source according to claim 3, wherein the discharge chamber contains a conductive material. The plasma discharge ion source according to claim 3, wherein the inlet is configured to simultaneously receive the plasma gas and a sample containing an analite. Further provided with a second entrance separate from the entrance
The plasma discharge ion source according to claim 3, wherein the second inlet is configured to supply a sample containing an analite to the discharge chamber. The discharge chamber has a first area adjacent to the at least one inlet, a third area adjacent to the at least one outlet, and a second area between the first area and the third area. The plasma discharge ionization source according to claim 3, further comprising an area. The plasma discharge ionization source according to claim 11, wherein the average inner diameter of the third area is larger than the average inner diameter of the second area. The plasma discharge ionization source according to claim 12, wherein the average inner diameter of the second area is larger than the average inner diameter of the first area. The plasma discharge ion source according to claim 1, wherein the discharge chamber further comprises a second inlet configured to receive a second plasma gas. The plasma discharge ion source according to claim 1, wherein the discharge chamber is configured to maintain the plasma discharge without any inductive coupling. A second discharge chamber fluidly coupled to the discharge chamber is further provided.
The plasma discharge ionization source according to claim 5, wherein the second discharge chamber includes at least one curved portion between an inlet area and an outlet area of the second discharge chamber. The plasma discharge ionization source according to claim 16, wherein the at least one curved portion of the second discharge chamber has a different geometric shape from the at least one curved portion of the discharge chamber. The plasma discharge ion source according to claim 17, further comprising an electrode electrically coupled to the second discharge chamber. The plasma discharge ion source according to claim 18, wherein the second discharge chamber is configured to maintain plasma discharge with a second plasma gas different from the plasma gas. The plasma discharge according to claim 1, wherein the discharge chamber is configured to receive two or more different plasma gases and use the different plasma gases to selectively ionize different analog species. Ionization source. A method comprising ionizing the analysts by introducing them into a plasma discharge maintained in a discharge chamber comprising a first electrode.
The discharge chamber comprises at least one inlet and at least one outlet.
The plasma discharge is maintained in the discharge chamber by supplying a voltage to the first electrode in the presence of plasma gas introduced into the discharge chamber through at least one inlet of the discharge chamber. The above method. 21. The method of claim 21, further comprising configuring the first electrode so that it is located within the at least one inlet of the discharge chamber. 22. The method of claim 22, further comprising supplying the first electrode with a DC voltage of about 10 volts to about 5000 volts. 22. The method of claim 22, further comprising supplying the first electrode with an AC voltage of about 20 to about 3000 volts. Further including supplying a radio frequency current to the first electrode,
22. The method of claim 22, wherein the radio frequency range of the radio frequency current is from about 100 Hz to about 10 MHz. 21. The method of claim 21, further comprising maintaining the plasma discharge in the discharge chamber at a pressure of about 10 ^{-3 to 100 torr.} 21. The method of claim 21, further comprising providing the plasma discharge using a plasma gas flow rate of 500 sccm or less. The discharge chamber in a first area adjacent to the at least one inlet, a third area adjacent to the at least one outlet, and a second area between the first area and the third area. Including further configuring
21. The method of claim 21, wherein the average inner diameter of the third area is larger than the average inner diameter of the second area. The supply voltage is selected so as to promote the production of the parental ananalyte ion of the ionized analyte and allow the quantification of the analyte using the mass vs. charge peak intensity of the parental analyte ion. 21. The method of claim 21. 21. The method of claim 21, further comprising monitoring the current supplied to the first electrode to determine if the plasma discharge is maintained in the discharge chamber. 21. The method of claim 21, further comprising using an optical sensor to determine if the plasma discharge is maintained within the discharge chamber. The plasma gas is one or more of helium, neon, argon, krypton, xenone, nitrogen, nitric oxide, ammonia, oxygen, air, compressed air, hydrogen, methane, carbon monoxide, carbon dioxide, or nitrogen dioxide. 21. The method of claim 21. Introducing the analysts into the discharge chamber and ionizing the introduced analysts using a first plasma gas.
Allowing the ionized analyst to exit the discharge chamber through the at least one outlet prior to introducing the second analyst into the discharge chamber.
Further, the introduction of the second announcer into the discharge chamber and ionization of the introduced second analyze using a second plasma gas different from the first plasma gas. 21. The method of claim 21. Allowing the ionized second analyst to exit the discharge chamber through the at least one outlet before introducing the third analyst into the discharge chamber.
The third analyst is introduced into the discharge chamber, and the introduced third analyst is used as the first plasma gas and a third plasma gas different from the second plasma gas. 33. The method of claim 33, further comprising ionizing the plasma. Each of the first plasma gas, the second plasma gas and the third plasma gas is helium, neon, argon, krypton, xenone, nitrogen, nitrogen monoxide, ammonia, oxygen, air, compressed air, hydrogen. , Independently selected from the group consisting of methane, carbon monoxide, carbon dioxide, and nitrogen dioxide,
34. The method of claim 34, wherein each of the first plasma gas, the second plasma gas and the third plasma gas comprises a different composition. The analysis is introduced into the discharge chamber and the introduced analysis is ionized using a first voltage supplied to the at least one electrode.
Allowing the ionized analyst to exit the discharge chamber through the at least one outlet prior to introducing the second analyst into the discharge chamber.
Further comprising introducing the second analyst into the discharge chamber and ionizing the introduced second analyst using a second voltage different from the first voltage. 21. The method of claim 21. Allowing the ionized second analyst to exit the discharge chamber through the at least one outlet before introducing the third analyst into the discharge chamber.
The third analyst is introduced into the discharge chamber and the introduced third analyst is ionized using a third voltage different from the first voltage and the second voltage. 36. The method of claim 36, further comprising: 37. The method of claim 37, further comprising modifying the composition of the plasma gas prior to introducing the second analyst into the discharge chamber. 21. The method of claim 21, further comprising configuring the discharge chamber to include at least one bend between the at least one inlet and the at least one outlet. Further comprising coupling the discharge chamber to a second discharge chamber
The second discharge chamber is electrically coupled to the second electrode.
The second discharge chamber comprises at least one inlet and at least one outlet.
21. The method of claim 21, wherein the plasma discharge is maintained in the second discharge chamber by supplying a voltage to the second electrode in the presence of plasma gas. Further forming the second discharge chamber having at least one curved portion between the at least one inlet of the second discharge chamber and the at least one outlet of the second discharge chamber. The method of claim 40, comprising. 21. The method of claim 21, further comprising maintaining the plasma discharge in the discharge chamber without any inductive coupling. It is configured to be fluidly coupled to at least one outlet of the discharge chamber of the plasma discharge ionization source according to any one of claims 1 to 20 and to receive ionized analysts from the discharge chamber. A mass spectrometer system with a mass spectrometer that has been used. The plasma discharge ionization source according to any one of claims 1 to 20 and
A kit comprising the instructions for providing plasma discharge into the discharge chamber using the plasma discharge ion source according to any one of claims 1-20. It ’s a way to promote the ionization of analite.
To provide said discharge chamber that is configured to maintain plasma discharge within the discharge chamber.
The discharge chamber is configured to electrically couple to at least one electrode that is configured to couple to a power source.
The discharge chamber further comprises at least one inlet and at least one outlet.
Including providing the discharge chamber
The method, wherein the discharge chamber is configured to maintain the plasma discharge within the discharge chamber using a voltage supplied to the at least one electrode. 45. The method of claim 45, wherein the discharge chamber further comprises at least one bend between the at least one inlet and the at least one outlet. A method of quantifying analysts in a sample
By using a plasma gas flow rate of 500 sccm or less, after introducing the allate into the plasma discharge generated in the discharge chamber, the peak intensity of the parent analite ion generated from the ionization of the allate is measured. Including
The method, wherein the plasma gas is selected to use the generated plasma discharge to increase the production of said parental analite ions. A method of ionizing an analysis to increase the production of parental analysis ions.
The plasma gas supplied to the discharge chamber and the voltage supplied to the discharge chamber are used to introduce the analysts into the plasma discharge maintained in the discharge chamber.
The plasma discharge is maintained in the discharge chamber using a plasma gas stream of 200 sccm or less.
The method, wherein the plasma discharge comprises an average temperature of about 2000 Kelvin or less. A plasma discharge containing an average temperature of about 2000 Kelvin or less.
The plasma discharge, wherein the plasma discharge is maintained in the discharge chamber using the voltage supplied to the discharge chamber in the presence of plasma gas supplied at a plasma gas flow rate of 200 sccm or less. The plasma discharge configured to provide both positive and negative analyze ions without changing the voltage supplied to maintain the plasma discharge.

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